Photographic element,composition and process having an s-carbamoyl stabilizer

ABSTRACT

S-CARBONYL SILVER SALT STABILIZER PERCURSORS ARE USEFUL IN PHOTOGRAPHIC ELEMENTS AND COMPOSITIONS FOR STABIILIZING AN IMAGE IN PROCESSING BY HEAT OR BY TREATMENT WITH AMMONIA OR AMINE VAPOR. THE PHOTOGRAPHIC ELEMENTS AND COMPOSITIONS CAN CONTAIN ADDENDA EMPLOYED IN PHOTOGRAPHIC MATERIALS SUCH AS SILVER HALIDE DEVELOPING AGENTS.

United States Patent 3,824,103 PHOTOGRAPHIC ELEMENT, COMPOSITION ANDPROCESS HAVING AN S-CARBAMOYL STABILIZER Zona R. Pierce and Grant M.Haist, Rochester, Jon T. Staples, Pittsford, and David A. Pupo,Churchville, N.Y1.\,I gzssignors to Eastman Kodak Company, Rochester, NoDrawing Filed May 8, 1972, Ser. No. 251,728

Int. Cl. G03c l/34 U.S. Cl. 96--109 12 Claims ABSTRACT OF THE DISCLOSURES-car-bamoyl silver salt stabilizer precursors are useful inphotographic elements and compositions for stabilizing an image inprocessing by heat or by treatment with ammonia or amine vapors. Thephotographic elements and compositions can contain addenda employed inphotographic materials such as silver halide developing agents.

BACKGROUND OF THE INVENTION Field of the Invention Description of theState of the Art The use of various sulfur-containing compounds asstabilizer precursors in photographic elements designed for processingwith heat is known. These are described, for example, in U.S. Pat.3,301,678 of Humphlett et al., issued Jan. 31, 1967; U.S. Pat. 3,506,444of Haist et al., issued Apr. 14, 1970; U.S. Pat. 3,573,048 of Boller etal., issued May '30, 1971; U.S. Pat. 3,531,285 of Haist et al., issuedSept. 29, 1970; and Belgian Pat. 763,751 issued Sept. 3, 1971. A usefulclass of stabilizer precursors includes compounds which are based onthiuronium derivatives as described in these references. In someinstances, the stabilizer precursors have not been entirely satisfactorybecause they often require higher than desired temperatures inprocessing of photosensitive materials designed for processing withheat. Temperatures of about 190 C. to about 220 C. have been employedwith such stabilizer precursors which has presented problems with thefilm support which is employed. Cellulose acetate film, for example, cansoften at about 100 C. and polyester film supports can undergodistortion at about 160 C. It has been desirable to provide stabilizerprecursors which enable use of lower processing temperatures.

Processing employing vapors of ammonia or amines has also been describedin the art. U.S. Pat. 2,410,644 of Fierke et al., issued Nov. 5, 1946describes employing ammonia or amines in processing of photographicelements containing a silver halide emulsion in a silver halidedeveloping agent. Development of the emulsion, however, does not takeplace in a substantially dry state but is carried out in the presence ofwater by the application of steam or water vapor. Moreover, anadditional step is required to stabilize the image. Processing employingammonia or amine vapors with incorporated thiuronium stabilizerprecursors is described in copending U.S. Appli- 3,824,103 Patented July16, 1974 cation Ser. No. 224,935 of King, filed Feb. 9, 1972, nowabandoned. There has been a continuing need to provide photosensitivematerials containing certain stabilizer precursors which can beprocessed with heat or with ammonia or amine vapors.

There accordingly has been a need to provide .photosensitive materialsand processes, such as processing with heat or ammonia or amine vapors,which enable substantially dry stabilization of a developed imagewithout subsequent processing steps.

SUMMARY OF THE INVENTION It has been found according to the inventionthat stabilization of a developed image as described can be provided bya stabilizing concentration of about 0.25 to about 20 moles per mole ofphotosensitive silver salt of an S-carbamoyl silver salt stabilizerprecursor in photosensitive silver salt elements, compositions andprocesses for stabilizing a developed image employing heat or ammonia oramine vapors. Such photosensitive materials which are designed forprocessing with heat containing the described S-carbamoyl silver saltstabilizer precursors enable lower processing temperatures to beemployed and/or improved.

DETAILED DESCRIPTION OF THE INVENTION A range of S-carbamoyl silver saltstabilizer precursors can be employed according to the invention. Onetest for suitable S-carbamoyl silver salt stabilizer precursors isdescribed in Example 1 wherein the S-carbamoyl silver salt stabilizerprecursor is employed in a photosensitive material for processing withheat. A test for suitable S-carbamoyl silver salt stabilizer precursorsin processing with ammonia or amine vapors is described in Example 2.

A useful class of S-carbamoyll silver salt stabilizer precursorsincludes compounds represented by the formula:

wherein R and R are each selected from the group consisting of hydrogen,alkyl, especially alkyl containing 1 to 5 carbon atoms such as methyl,ethyl, propyl, butyl and pentyl, aryl, e.g. phenyl and tolyl; and SR isa sulfur containing moiety which has the property of cornplexing withphotosensitive silver halide in the presence of heat or alkali. Thealkyl and aryl radicals and the sulfur containing moiety can containsubstituent groups which do not adversely affect stabilizing action ordesired properties of the described silver salt stabilizer precursor orthe photosensitive material in which the precursors are employed.Typical examples of substituent groups which do not adversely afiect theactivity of the stabilizer precursor include methyl, ethyl, propyl,isopropyl, tertiary butyl and n-butyl. The described compounds alsoinclude salts of such compounds, such as amine salts, which do notadversely aifect the activity of the stabilizer precursor. The describedsulfur-containing moiety which has the property of complexing "withphotosensitive silver halide in the presence of heat and/or alkali, is amoiety which will cleave or be released from the described carbamoylstabilizer precursor at elevated temperatures or in the presence ofalkali such as ammonia or amine vapors and complexes or combines with aphotosensitive silver salt such as photosensitive silver halide inunexposed areas of a photosensitive silver salt material, such as aphotosensitive silver halide emulsion, forming a mercaptide compoundwhich is more stable to light, atmospheric conditions and ambienttemperatures than the photosensitive silver salt. A suitablesulfur-containing moiety which has the property of complexing withphotosensitive silver halide in the presence of heat or alkali includesa moiety represented by the formula:

wherein R is amino, alkyl, especially alkyl containing 1 to 4 carbonatoms such as methyl, ethyl, propyl and butyLcarboxyl, carboxyalkylcontaining 2 to 5 carbon atoms, such as carboxymethyl, carboxyethyl, andcarboxypropyl, aminomethyl, sulfoalkyl containing 1 to 4 carbon atoms,e.g. sulfornethyl and sulfoethyl, morpholinomethyl, or a grouprepresented by the formula:

SOs

SCHCOOH A range of carbamoyl moieties can be employed in the describedS-carbamoyl stabilizer precursors. Examples of suitable carbamoylmoieties include the following:

ll --CNHCH2CH2 O CHzCHa I] -CN CHzCHa C NHOHZOHZCHgCHZ TypicalS-carbamoyl silver salt stabilizer precursors include compoundsrepresented by the formula:

wherein R is hydrogen or alkyl containing 1 to 5 carbon atoms; R isselected from the group consisting of alkyl containing 1 to 5 carbonatoms, phenyl and benzyloxy; R is amino, alkyl containing 1 to 4 carbonatoms, carboxyl, carboxyalkyl containing 2 to 5 carbon atoms,aminomethyl, sulfoalkyl containing 1 to 4 carbon atoms such assulfomethyl and sulfoethyl, morpholinomethyl, or

wherein R is alkyl containing 1 to 4 carbon atoms; R is hydrogen oralkyl containing 1 to 4 carbon atoms; and R is hydrogen or carboxyl.These compounds include salts such as amine salts which do not adverselyaffect the activity of the stabilizer precursor.

In certain cases the S-carbamoyl silver salt stabilizer precursor can bea polymer containing the S-carbamoyl moiety. A suitable polymercontaining the S-carbamoyl moiety is cop0ly[viuyl methylether-N-(ethylcarbamoylthioethyl)ma1eamic acid]. In instances where anS-carbamoyl silver salt stabilizer precursor which is a polymer isemployed, the polymer can replace part of a binder or vehicle employedin the photosensitive material in which the stabilizer precursor isemployed.

Especially useful S-carbamoyl silver salt stabilizer precursors include:5

S-ethylcarbamoyl-Z-mercaptoisobutyric acid, dicyclohexylamine salt,S-ethylcarbamoyl-Z-mercaptoethylamine, p-toluene sulfonic acid salt,fl-(Ethylcarbamoylthio)propanesulfonic acid, guanidinium salt, andS-ethylcarbamoyl-N-acetyl-Z-mercaptoethylamine.

The described S-carbamoyl silver salt stabilizer precursors can beprepared by procedures known in the art. For instance, proceduresdescribed in St. Guttmann, Helv. Chem. Acta, 40:83 (1966) are suitable.

The described S-carbamoyl silver salt stabilizer precursors can beemployed in a range of physical locations in a photographic system. Theycan be employed in one or more layers of a photographic element and/orin a processing composition if desired. The optimum location will dependupon the desired image, processing conditions, particular photographicsystem and the like. The S-carbamoyl silver salt stabilizer precursorsare preferably employed in a location contiguous to the photosensitivecomponent which is to be stabilized. For example, the stabilizerprecursors can be incorporated into one or more layers of a photographicelement such as a photographic silver halide emulsion layer, a layerbetween the support and the photographic silver halide emulsion layer,and/ or an overcoat layer.

One embodiment of the invention is a photographic element comprising asupport having thereon a photosensitive silver salt and an S-carbamoylsilver salt stabilizer precursor as described. A range of concentrationof the described silver salt stabilizer precursor can be employed in aphotographic element depending upon the desired image, developing agentemployed, processing conditions, particular stabilizer precursor and thelike. The concentration of stabilizer precursor which is suitable isusually at least about 0.25 moles of the stabilizer precursor for eachmole of photosensitive silver salt present to be stabilized. Suitableconcentrations include about 0.25 moles to about 20 moles of thestabilizer precursor for each mole of silver halide. However, it isoften desirable to use molar excesses of the stabilizer precursor toassure effective stabilization of the photosensitive silver salt to bestabilized. In some cases it can be desirable to employ at least 5 to 10times the required amount of stabilizer precursor.

Various photosensitive silver salt materials can be stabilized employingthe described stabilizer precursors. Typically the photosensitive silversalt materials are photosensitive silver halide materials. These includeany photosensitive silver halide such as silver chloride, silverbromide, silver bromoiodide, silver chlorobromoiodide or mixturesthereof. The silver halide materials which are suitable are described,for example, in the Product Licensing Index, Vol. 92, December 1971,publication 9232, pages 107-110 in paragraphs I, II and III. Aphotosensitive silver halide useful in the invention can be chemicallysensitized as described in paragraph III of this Product Licensing IndexPublication.

The photosensitive silver halide materials and compositions according tothe invention can contain various addenda which do not adversely affectthe stabilizing action of the described stabilizer precursors. Theseinclude development modifiers, antifoggants, hardeners, plasticizers andlubricants, coating, aids, matting agents, brighteners and spectralsensitizing dyes as described in the Product Licensing Index, Vol. 92,December 1971, publication 9232, pages 107-110. The photographicelements useful according to the invention can contain antistatic andconducting layers and light-absorbing and filter dyes as described inthis publication.

Another embodiment of the invention is a photosensitive compositioncomprising a photosensitive silver salt, such as photosensitive silverhalide, and an S-carbamoyl silver salt stabilizer precursor asdescribed.

A photographic element and/ or composition described according to theinvention can contain various colloids alone or in combination asvehicles, binding agents and in various layers. Typically hydrophilicmaterials are employed in those instances where aqueous solutions are tobe used in processing. However, in those instances in which thephotosensitive material is for processing with heat, a hydrophobicbinder can be used. Accordingly, hydrophilic and/ or hydrophobicmaterials can be employed as binders depending on the particularphotosensitive material and the intended processing. Suitablehydrophilic materials include naturally-occurring substances such asproteins, for example, gelatin, gelatin derivatives, cellulosederivatives, polysaccharides, such as dextran, gum arabic and the like;and synthetic polymeric substances such as water soluble polyvinylcompounds like poly(vinyl pyrrolidone), acrylic polymers and the like.Other synthetic polymeric compounds which can be employed includedispersed vinyl compounds such as in latex form and particularly thosewhich increase dimensional stability of photographic materials. Suitablesynthetic polymers include those described in the Product LicensingIndex, Volume 92, December 1971, publication 9232, pages 107- 110 inparagraph VIII.

The photosensitive materials and other layers of a photographic elementaccording to the invention can be coated on a wide variety of supports.Typical supports include cellulose nitrate film, cellulose ester film,poly- (vinyl acetal) film, polystyrene film, poly(ethyleneterephthalate) film, polycarbonate film and related films or res inousmaterials as well as glass, paper, metal and the like. Typically aflexible support is employed, especially a paper support which can bepartially acetylated or coated with baryta and/or an alpha olefinpolymer particularly a polymer of an alpha olefin containing 2 to 10carbon atoms such as polyethylene, polypropylene, ethylenebutenecopolymers and the like.

The photosensitive silver salt materials employed according to theinvention can be X-ray or other non-spectrally sensitized material orthey can contain spectral sensitizing dyes as described.

The sensitizing dyes and/or other addenda such as the describedstabilizer precursors according to the invention, can be added fromwater solutions or suitable organic solvent solutions can be used. Thecompounds can be added using various procedures known in thephotographic art as described in the aforesaid Product Licensing IndexPublication.

The described stabilizer precursors can be employed in combination withany silver salt developing agent or developing agent precursor whichdoes not adversely alfect the stabilizing action of the stabilizerprecursor and which provides the desired developing activity. Suitablesilver halide developing agents which can be employed in combinationwith the stabilizer precursor described include, for example,polyhydroxybenzene developing agents such as hydroquinone,alkyl-substituted hydroquinones as exemplified by tertiarybutylhydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone and2,6-dimethylhydroquinone, catechols and pyrogallol; chloro-substitutedhydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxysubstituted hydroquinones such as methoxyhydroquinone orethoxyhydroquinone; aminophenol developing agents such as2,4-diaminophenols and methylaminophenols; ascorbic acid developingagents such as ascorbic acid, ascorbic acid ketals and other ascorbicacid derivatives; hydroxylamine developing agents such asN,N-di(2-ethoxyethyl)-hydroxylamine; 3-,

pyrazolidone developing agents such as 1-phenyl-3-pyrazolidone and/or 4methyl-4-hydroxymethyl-l-phenyl-3- pyrazolidone; and the like.

A range of concentration of the described developing agents can beemployed wtih a range of concentrations of the described stabilizerprecursor. A typical concentration range of the described silver halidedeveloping agent is about 2 moles to about 1 mole of the silver halidedeveloping agent per mole of photosensitive silver halide to bedeveloped.

The described silver halide developing agents can be employed in a rangeof photographic processing compositions, such as in photographic silverhalide developer compositions, hardener compositions, monobaths and thelike which can be employed in processing of a photographic elementcontaining the described stabilizer precursor. The described silver saltdeveloping agent can be employed in addition in the describedphotographic element.

After exposure, the resulting latent image in a photographic elementcontaining the described stabilizer precursor and a suitable silver saltdeveloping agent, as described, can be developed and stabilized bycontacting the element with an alkaline development activator.Especially suitable alkaline development activators include ammonia oramine vapors. Vapor processing employing ammonia or amine vapor whichcan be performed according to the invention is suitable for singleexposure holographic interferometry. This procedure is described, forexample, in the Principles of Holography by Howard H. Smith, 1969, JohnWiley, New York, N.Y. Employing ammonia or amine vapors for processingthe latent image can be developed and stabilized at a range oftemperatures and time. Typically vapor processing is carried out so asto provide a developed and stable image at about 15 C. to about 70 C.within about one to about 60 seconds.

Other development activators which can be employed in the practice ofthe invention include any of those which are alkaline developmentactivators such as inorganic alkalies including, for example, sodiumhydroxide, potassium hydroxide and/or lithium hydroxide, alkali metalcarbonates such as sodium carbonate and potassium carbonate, alkalimetal phosphate, such as trisodium phosphate and/or organic alkalinedevelopment activators such as quaternary ammonium bases and salts aswell as amino alkanol and similar alkaline materials and/or alkalinerelease materials. The described development activators can be appliedto the described photographic element containing the developed image andthe stabilizer precursor in any suitable manner including, for example,dipping, spraying and/or suitable surface applications such as withrollers or other mechanical means.

The pH of the composition which is sufficient to activate the describedstabilizer precursor and a developing agent should be sufiicient toprovide a pH of about 8.0 to about 13.0.

Concentrations of moisture can be present in the described photographicelements which are usually present in conventional photographic papersupports under ordinary conditions, such as at 25 C. at 40% relativehumidity. Small concentrations of moisture can provide beneficialeffects in aiding the cleaving action of the described stabilizerprecursor.

Another embodiment of the invention is a photographic process fordeveloping and stabilizing an image in a photographic element comprisinga support having thereon a photosensitive silver salt, a silver saltdeveloping agent,

and an S-carbamoyl silver salt stabilizer precursor as decomprising asupport having thereon a photosensitive silver salt and an S-carbamoylsilver salt stabilizer precursor comprising heating the photographicelement to about C. to about 200 C. until the desired stabilized imageis provided.

By increasing or decreasing the length of time of heating, a higher orlower temperature within the described range can be employed. Typicallya developed and stable image is provided within about one to about 60seconds.

Any suitable means can be used for providing the desired processingtemperature range. The heating means can be a simple hot plate, rolleror the like.

The following examples are included for a further understanding of theinvention.

Example 1 A photosensitive composition is prepared by mixing thefollowing components:

Gelatitn (pigskin gelatin, 12% by weight gelatin in aqueous 50 ml.

solu on Surfactant (10% by weight in aqueous solution), alkyllml.

ohenoxypoly(hydroxypropyleneoxide).

S-methylbenzotriazole. 0.1 g.

Gelatino silver chloride emulsion (a fine-grain silver chloride 10.0 ml.

gelatino emulsion in which the silver halide is predominantly silverchloride as described in British Patent. 1,063,844) (42 mg. of silverper ml.).

Bis(vinylsu1fonylrnethyl) ether 0.2 g-

After mixing, the resulting composition is coated on a polyester filmsupport at 45 milligrams of silver per square foot. The resultingphotographic element is sensitometrically exposed to tungsten light. Theexposed photographic element is processed by contacting the side of thephoto graphic element opposite the photosensitive coating with a heatedmetal block at C. for 15 seconds. A light stable, developed image isproduced having a black tone with a transparent background and having astraight line gamma of 0.75 with a maximum density of 1.2.

In the absence of the described carbamoyl compound in the photographicelement, the image developed is unstable producing darkening uponexposure to light.

Example 2 The procedure set out in Example 1 is repeated with theexception that after sensitometric exposure the photographic element istreated with ammonia fumes for 90 seconds at about 20 C.

A developed stable image having a clear background is produced with agamma of 1.2 at a maximum density of 1.4.

Example 3 The procedure set out in Example 1 is repeated with theexception that the photographic element after sensitometric exposure isprocessed by immersion for 10 seconds in an aqueous alkaline solution at20 C. containing 5% by weight sodium hydroxide, 10% by weight sodiumsulfite and 5% by Weight sodium sulfate. The photographic element afterprocessing is squeegeed to remove excess processing solution but is notwashed before drying. The resulting developed stable image has a minimumdensity of 0.06, a maximum transmission density of 0.63 and a gamma of0.46.

Higher transmission densities are obtained by rebalancing the componentsof the photographic element for this type of solution processing. Noattempt is made to provide optimum concentrations of components in thisexample.

i 9 Examples 4-33 A coating composition is prepared by mixing thefollowing components:

Gelatin (pigskin gelatin, 12% by weight in aqueous solution) 50 ml.

Surfactant (surfactant from Example 1, 10% by weight in aqueoussolution) lml. Stabilizer precursor 0.01% of molecu- 10l-phenyl-B-pyrazolidone lar weight. S-methylbenzotriazole 1 g.

Photographic silver chloride emulsion 0.1 g.

(42 milligrams of silver per ml.) 10 ml.

The stabilizer precursors employed in this composition are listed in thefollowing Table I."

A photographic element is prepared employing this composition by coatingon a polyester film support at a concentration of 45 milligrams ofsilver per square foot.

The resulting photographic element is sensitometrically exposed totungsten light. The exposed photographic element is then processed bycontacting the side of the element opposite the photosensitive coatingon a heated metal block at 160 C. for 15 seconds. The results and thestabilizer precursor as well as any composition variation is listed infollowing Table H.

TABLE I I 13? Name Structure 1 S-(N-ethylaminocaroonyD-L-cysteine OCHaCHzNH'J-S-CHrCHC 0 011 2 SgfiyicarbamoyH-mercaptopropionic acid,dicylohexylamine CHsCHzNHC-S-CHCO 0- HI H2(C| u)1 3B-ggzylcarbamoyl-3-mercapto-propionic acid, dicyclohexylamineCH:CHaNHCS-CH:CH;C 0 0" NHzWuHu): 4 S-ethyicarbamoyl-2mereaptoisobutyr1cacid, dieyclohexylamine 0 CH;

salt omcnmnd-s-c-coo- I fi awcHnh 5S-ethylcarbamoyl-2,2-dimethyl-B-mercaptopropiouic acid, 0 H;

dieyclohexylamine salt. I] I Y CHlCHBNHC-'SCHICCOO' H: Ha( |Hu):

6 Copoly 1 [vinyl methyl ether-N-ethylcarbamoyl(thioethyl) C O OHmaleamic acid]. CHlCH (([IH C H) :0 (3H1 I IH H CH; SC--NH-CH;CH1

7 S32110arbamoyl-Z-mercaptoethylamine, p-toluenesuli'onic acid %0CH;CHNHC S-C HaCHgNHg 8 S-ethylcarbamoyl-Z-mercaptopropionic acid. %0

CH:CHzNHC--SCHC 0 OH (I) H; 9...-:.....3-(ethylcarbam0y1thi0)pr0panesulfonic acid, sodium salt. .:-:.z:; O

CHxCHzNH9-S-CH:CH:CH S OINQ 10.....n:.s-gfinylearbamoyl-2-mercaptoethylamine, p-toiuenesulionie acid Seefootnote at end of table.

TABLE I-Continued C d. N8. Name Structure 2 2-[3-(ethoirycarbonylmethyl)ureido1ethyl N-(ethoxy carbonylmethyDthiocarbamate. ll llCHaCHz-CCH:NHOS-CHnCHiNHCNH- (I? -CHC-OCHCH;

23 N-(ethylcarbamoylthioethyl)-N-methylmorphollnium p-toluene- O CH;

sulfonate. H

CHsCHaNHC-S-CHzClh-N 1 Dilficulty is encountered in coating thiscompound.

TABLE II Silver Comcoverage Image density ound Ex. Composition mg. o.No. variation Ag it!) Dmax, Dmi... Light stability Background Remarks 447. 5 0. 73 0W Light stable in sec., at 140 C. 5 0 5X stab. 48.1 0.58 6GAL..- 45.5 0.84 Light stable in 5 see., 140 C. 7 GAL..... 41.4 0.57 Do.8 GAL 48.4 0.72 Do. 9 GAL 49.5 0.95 Poor coating (low 501.). Lightstable in 5 sec., at 140 C. 7 10 GAL 88.7 0.95 Almost light stable in 10sec. at 140 C, 7 11 41.4 1.00 Almost light stable in 10 sec, at 140 OBrown image, clear background with yellow tint with 60 second ammoniatreatment. 12 43. 2 1.14 0.06 .do Transparent hazy. Almost light stablein 20 seconds, 140 C. 13 43. 3 1. 26 0. 07 -....do -.do Almost lightstable in seconds, 140 C. 14 46.7 0.62 0.16 Partially stabilized. 15 .80. 28 0.12 Stable Transparent hazy- Uneven: c gggigg. Almost light stablin 15 see. a 16 5-MBTAZ 43.1 0.92 0.10 Partially stabilized. 17 fi-MBTAZ42.0 0.92 0.07 Stable Transparent hazy. Light stable in 15 sec. at 140C, Al t light stable in 15 sec. at 130 C. 1s 5-MBTAZ,1.33X 42.1 0.940.09 do Pale tan; hazy....- Light stable in 15 sec. at 140 0, Almoststab. light stable in 15 sec. at 130 C. 19 5-l;igAtZ,bASC, 40.6 0.780.20 -do Tan; hazy s a 20 fi-MBTAZ 36.0 0.85 0.06 ...-..d0 Clear Lightstable in 15 sec. at 140 0, Al t light stable in 15 see. at 130 C. 215-MBTAZ 41.3 1.22 .do Orange...-: 22 5-MBIAZ,PTP 45.3 1.05 do 23 s-MBTAZ38.7 1.38 do Yellow-tan: almost opaque. 24 S-MB'IAZ. 36.0 0.85 ClearLilgihltltstgbtlfi iin see. a; 140 C. llmost sa e 11 soon sat130 255-MB'lAZ 41.3 1.22 Orange g e 26 5-MB'IAZ,PTP 45.3 1.05 do 27 S-MBTAZ38.7 1.38 0 Yellow-tanalmost;

opaque. 28 5-MBTAZ.....' 39.4 0.12 0 Very paleyellow; Pie-stabilized.-

azy. 29 5-MB1AZ 41.3 0.70 0 Almostl' ht t b i 1 30 s 40.6 L07 0 ig s alo n 5sec at 140 C 31 fi-MBTAZ... 38.0 0.50 0 32 5-MBTAZ 40.0 0. 93 0Poor coating (granular). 33 b-MBTAZ 45.0 0. 70 0 Light stable in 15 sec.at 140 0. Almost light stable in 15 sec. at 130 C.

l G AL=D-ga1actonamlde (3 grams): 0.5X stab. 0.33 stab.=% or 36stabilizer level indicated in example: 5-MBTAZ=0.1 ram additional 5-methlbenzotrlazole; PlP =phenidone replaced with2-propy1-4,5,6-trlhydroxypyrimidine (1 gram); ASC=acetone semicarbazonegrams). y

1 (Comparative example.)

tures of about 130 C. it is usually desirable that the structure of thecarbamoyl compound not contain a carboxyl or sulfonate group ifincreased stability of the developed image to light is to be obtainedwithin a reduced processing time.

The S-ethylcarbamoyl-Z-mercaptoisobutyric acid, dicyclohexylamine saltproduces an unusually clear and colorless background in the describedphotographic element.

In general, activation of the described photographic element withammonia produces a higher maximum density and higher contrast thanprocessing with heat.

In some instances a further advantage of certain of the carbamoylstabilizer precursors as described is provided when the sulfur moiety isan antisludging agent upon release from the carbamoy'l moiety. Suchantisilvering and/or antisludging activity is provided when thecarbamoyl moiety is released from an antisludging agent such asZ-mercaptoisobutyric acid. Release of small concentrations of theantisludging agent into the processing solution during processing canprovide inhibition of silvering.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

What is claimed is:

1. A photographic element comprising a support having thereon aphotosensitive silver salt in association with a stabilizingconcentration of about 0.25 to about 20 1 moles of an S-carbamoyl silversalt stabilizer precursor per mole of said silver salt.

2. A photographic element as in claim 1 wherein said S-carbamoyl silversalt stabilizer precursor is a compound represented by the formula:

wherein R and R are each selected from the group consisting of hydrogen,alkyl containing 1 to 5 carbon atoms, phenyl, and tolyl, and S-R is asulfur containing moiety which has the property of complexing withphotosensitive silver halide in the presence of heat or alkali.

3. A photographic element as in claim 1 wherein said S-carbamoyl silversalt stabilizer precursor is a compound represented by the formula:

wherein R is hydrogen or alkyl containing 1 to 5 carbon atoms; R isselected from the group consisting of alkyl containing 1 to 5 carbonatoms, phenyl and benzyloxy; R is amino, alkyl containing 1 to 4 carbonatoms, carboxyl, carboxyalkyl containing 2 to 5 carbon atoms;aminomethyl, sulfomethyl, morpholinomethyl, or

o -oH2NHi JNH-R wherein R is alkyl containing 1 to 4 carbon atoms; R ishydrogen or alkyl containing 1 to 4 carbon atoms; R is hydrogen orcarboxyl.

4. A photographic element as in claim 1 wherein said S-carbarnoyl silversalt stabilizer precursor is copoly[vinyl methylether-N-(ethylcarbamoylthioethyl)maleamic acid].

5. A photographic element as in claim 1 wherein said S-carbamoyl silversalt stabilizer precursor is a compound selected from the groupconsisting of S-ethylcarbamoyl-2-mercaptoisobutyric acid, dicyclo'hexylamine salt, B-ethylcarbamoyl-2-mercaptoethylamine,p-toluenesulfonic acid salt, 1 Beta-(Ethylcarbamoylthio)propanesulfonicacid guanidinium salt, andS-ethylcarbamoyl-N-acetyl-Z-mercaptoethylamine.

6. A photosensitive composition comprising a photosensitive silver saltin association with a stabilizing concentration of about 0.25 to about20 moles of an S-carbamoyl silver salt stabilizer precursor per mole ofsaid silver salt.

7. A photosensitive composition as in claim 6 also comprising apolymeric binder.

8. A photosensitive composition as in claim 6 wherein said S-carbamoylsilver salt stabilizer precursor is a compound represented by theformula:

wherein R and R are each selected from the group consisting of hydrogen,alkyl containing 1 to 5 carbon atoms, phenyl, and tolyl, and R is asulfur containing moiety which has the property of complexing withphotosensitive silver halide in the presence of heat or alkali.

9. A photosensitive composition as in claim 6 wherein said S-carbamoylsilver salt stabilizer precursor is a compound represented by theformula:

wherein R is hydrogen or alkyl containing 1 to 5 carbon atoms; R isselected from the group consisting of alkyl containing 1 to 5 carbonatoms, phenyl and benzyloxy; R is amino, alkyl containing 1 to 4 carbonatoms, carboxyl, carboxyalkyl containing 2 to 5 carbon atoms,aminomethyl sulfoalkyl containing 1 to 4 carbon atoms, morpholinomethyl,or i S-ethylcarbamoyl-Z-mercaptoisobutyric acid, dicyclohexylarninesalt, tS ethylcarbamoyl-Z-mercaptoethylamine, p-toluenesulfonic acidsalt, Beta-(Ethylcarbamoylthio)propanesulfonic acid guanidinium salt,and S-ethylcarbamoyl-N-acetyl-Z-mercaptoethylamine.

112. A photosensitive composition as in claim 6 which is a photographicsilver halide emulsion.

References Cited I UNITED STATES PATENTS 3,647,439 3/1972 Bass 96-48 PD3,144,336 8/1964 Herz 96-109 3,615,617 10/1971 Cologne 96-109 3,598,5988/1971 Herz 96-109 3,365,294 1/1968 Konig 96-109 3,640,719 2/1972 Konig96-109 RONALD H. SMITH, Primary Examiner J. L. GOODROW, AssistantExaminer US. Cl. X.R. 96-76 R mg t 6mm STArss PATENT omcs CERTIFICATE OFCORRECTION Patent No. 3,821,103 Dated July 16, 197A Zona R. Pierce,Grant M, Haist,

Jon T. Staples and David A. Pupo,

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 3, lines 3-6, the structure should read as follows:

36 s c R Column 7, line 23, vapor" should read -----'vapo:v."s-----aColumn'g, lines 10-1 should read as follows:

stabilizer precursor 0.01% of molecular weight l-phenyl-3-pyrazolidone lg.

5 methylbenzotriazole 0.1 g.

photographic silver chloride 10 ml.

emulsion (42 milligrams of silver per ml) Column 9, Compound 1, "S-(N-ethylaminocarconyl)-L- cysteine" should read ---S-(N-ethylaminocarbonyl.)L-cysteine-----. Column 9, Compound 2,"dicylohexylamine" should read ---dicyclohexylamine---.

Column 11, Compound 20, "20" should read 2o---.

sighed and sealed this 26th day of November 1974,

QsE L) Attest:

C. MARSHALL DANN Commissioner of Patents McCOY M. GIBSON JR, 7Attes'cing Officer

